Oil and natural gas conversion process



May 17, 1932. l. N. BEALL OIL AND NATURAL GAS CONVERSION PROCESS 2 Sheets-Sheet 1 A Filed Oct. 15, 1929 I I I I I I May 17, 1932. l. N. BEALL OIL AND NATURAL GAS CONVERSION PROCESS Filed Oct. 15, 1929 2 Sheets-Sheet 2 Patented May 17, 1932 UNITED STATES PATENT OFFICE ISAAC N. BEALL, WASHINGTON, DISTRICT OF COLUMBIA, ASSIGNOB TO JOHN C. W.

BEALL, OI WASHINGTON, DISTRICT OF COLUMBIA OIL AND NATURAL GAS CONVERSION PROCESS Application filed October 15, 1929. Serial No. 23 99,801.

My invention relates to a process for converting hydrocarbons, such as mineral oils or constituents thereof, and natural gas or constituents thereof, into new and useful commercial products such as motor fuels.

While motor fuel is specifically mentioned as one of the products of conversion, I do not wish to limit myself to the production of any specific product, as one of the advantages of my process is its extreme flexibility, and by variations in operating conditions, which will be apparent to one skilled in the art, lighter, heavier or intermediate products such as kerosene, fuel oil and lubricating oil may be obtained.

Furthermore, while I preferably employ natural gas as one of the initial constituents undergoing treatment, other gaseous hydrocarbons are contemplated within the scope of my invention. The invention further contemplates the production of partial oxidation products from natural gas or other normally gaseous hydrocarbons, or gases containing the same by reaction with air or an oxidizing gas under controlled temperature and pressure conditions. This partial oxidation product may be used for the subsequent production of motor fuel, etc., by reaction with a non-oxidized hydrocarbon according to the preferred embodiment of my invention, or may be employed directly for other industrial uses. The invention also contemplates the production of motor fuel or similar products by reacting an oxidized hydrocarbon produced preferably by oxidizing natural gas, but which may be obtained from other sources. with an unoxidized hydrocarbon, preferably in the full vapor phase under pressure in the presence of an inert gas.

The primary object of the invention is to produce motor fuel or other valuable mate? rials by utilizing residuum oil and dry natural gas. By dry natural gas is meant gas consisting principally of the chemical constituents methane. ethane. propane and isobutane in varying proportions.

In order to effect a chemical conversion or combination between natural gas and oil by this method, it is desirable first to prepare a partial oxidation product from the natural concerned. The reaction between this oxidized material and oil takes place best in the full vapor phase and under pressure substantially above atmospheric. In order to produce full vapor phase, an inert gas such as may be injected nitrogen preliminary to the 'final zone of heat. Previously vapor phase has only been operated at comparatively low pressures and at high temperatures.

Of the two systems of treating oil, as heretofore practiced, vapor phase and liquid phase, vapor phase operates at a high temperature and low pressure, but produces 'a motor fuel of better quality and anti-knock value. This is offset by low yield. On the other hand, the liquid phase hgh pressure 30 process produces a greater yiel of gasoline of poorer quality and less anti-knock value. The oil gas conversion process of the present invention has the combined advantages of both the liquid and vapor phase processes,

inasmuch as the vapor phase is maintained under high pressure.

An additional advantage is gained by the ,action of the oxidized hydrocarbon material prepared from the natural gas. The process is not one of hydrogenation comparable to the Bergius process, but is rather one of dehydrogenation, because the combined oxy en of the oxidized hydrocarbon removes hy rogen from an unoxidized hydrocarbon oil and combines with what would otherwise be free carbon to form ring compounds, carbon dioxide and carbon monoxide, water and products of partial oxidation. The entire effect is beneficial as far as the production and quality of motor fuel is concerned, because practically all of the aromatic series fall within the range of motor fuel, and the aromatic members of the series are noted as antiknock compounds.

The process may be characterized as a con version process as distin ished from the ordinary cracking or disti lation processes. It is distinguished from ordinary conversion processes by the fact that it involves a reaction between a non-oxidized h droearbon and an oxidized hydrocarbon w ile in full vapor phase and under elevated pressure and temperature conditions, preferably in the presence of an inert gas.

I wish to stress particularly the commercial solution of the problem of oxidizing saturated gaseous hydrocarbons by the use of alr. Secondly, the specific action of a product of partial oxidation upon an oil while an the full vapor phase and under elevated conditions of temperature and pressure. Another advantage of the process is the fact that the exothermic heats of reaction reduce the amount of auxiliary heat that would be necessary otherwise.

The process involves several improved steps which combine to produce improved industrial results, and several of the steps of the process are themselves individually novel. Consequently, while I will descrlbe an improved process as a whole in the manner in which I prefer to carry it out, it will be apparent that I do not intend to lunit my invention to the specific details to be hereinafter enumerated.

In carrying out my improved process, a hydrocarbon material, such as, for example natural gas, is heated under pressure, and air, or an oxygen-carrying gas, is separately heated, likewise under pressure, and the two heated gases are then contacted within a reaction zone. In carrying out the reaction the hydrocarbon material and the oxygencarrying gas are preferably heated in a continuous heater or heaters of tubular design. From the reaction zone the gases and vapors are passed immediately into a zone of constant temperature. From the constant temperature zone, the reaction materials pass through knock-out or separating apparatus for the separation of liquid material.

Following the removal of liquid in the separator the gases and vapors are preferably passed into an absorber, where they are contacted with oil which-is supplied to the absorber under pressure. This absorber may be of any standard design capable of withstanding the necessary pressure. The gases and vapors are, by this absorption step, stripped of practically all their constituents, with the exception of inert gases, such as, for example, nitrogen.

The oil, together with the absorbed material from the absorber and all the oxidized hydrocarbon liquids from the knock-out or separator, pass into a mixing chamber where there is added a stream of vapors diverted from the main absorption step. Preferably from this stage the admixed vapors and oil pass through a zone of gentle heating, where the entire mixture is converted into the vapor phase prior to entering the final stage of heating. In the final stage of heating the desired reaction temperature is obtained The reaction materials then pass into an enlarged space or reaction chamber or zone where sufiicient time is allowed for the completion of conversion initiated in the final stage of heating.

Having hereinbefore described in a generalway some of the important features of this process, I will now describe one specific method by which a person or persons skilled in the art may obtain certain desired results. It must be understood that this description is by way of illustration and that this process is by no means limited to this specifically described procedure.

For raw materials I may use (1) natural gas stripped of hydrocarbons suitable for constituent of motor fuel, (2) air, and (3) gas oil of thirt -five degrees Baum. The proportions 11sec of each may be in the following ratio: forty cubic feet of gas, fifty cubic feet of air, and one gallon of gas oil.

The gas and air may be separately compressed in two stages of compression as indicated in Fig. 2 to above 250 lbs.. and preferably about 300 lbs. per square inch, or the gas and air may be compressed at this time to the final stage of compression, around 1200 to 1250 lbs. per square inch. The gas and air under compression pass through separate heating coils where the temperature is raised to from 360 to 420 degrees Fahrenheit, and preferably about 400 degrees Fahrenheit. While at this temperature, the gas and air are contacted in a reaction chamber by jetting the air in counter current to the entering gas. This is done by manifolding both air and gas into tubes of small diameter and of less square area than the total square area of the pipes in which they were separately heated. The cubical contents'of the reaction zone is designed to meet the requirements of the plant. It is so constructed as to give a definite time of reaction with due allowance for time of admixture and increase of temperature. This reaction time is in the order of one-tenth to one second of time. A catalyzer such as nitrous oxide in the proportion of one to two per cent of the volume of hydrocarbon gas used is beneficial in promoting and completing the reactions. Sponge platinum also assists in the reactions.

The reaction involved is exothermic in nature, and therefore means have to be provided for conducting away the heat generated. This is done by passing the reaction products through a zone of constant temperature. A great many tubes of small diameter surrounded by steam under pressure of 500 lbs. per square inch, through which the gas is passed, serve-this purpose. These reaction products, (vapors and gases.) pass through a knock-out where some liquid is separated. If desired, the heated products may be employed for preheating the incoming gases by the use of suitable heat exchange appara-' tus (not shown). The uncondensed material passes through a third stage of compression, where the pressure is raised preferably to around 1200 to 1250 lbs. per square inch. If desired, the pressure may be originally raised to around 1200 to 1250 lbs. per square inch prior to the admission of the gas and air to the reaction chamber. While under this compression, these products pass through an absorption step, preferably of the countercurrent type, where the ascending gas meets the descending stream of oil. This strips the gas of all its low partial pressure material, and the vented gas consists mostly of nitrogen. As there is a great deal of free energy left in the nitrogen after this amount of compression, it can be made to perform work in the way of driving turbines,motors or pumps, or it may be used upon expansion for purposes of refrigeration and cooling. The oil, together with the absorbed material, passes through steps previously described. This includes passing through a heat exchanger,

then through a steam-to-oil preheater, where the temperature is raised to 500 degrees Fahrenheit. and then passes through a final stage of heating, where the temperature is preferably raised to approximately 785 degrees Fahrenheit. Following this final stage of heating, the reacting mixture then passes into an insulated reaction chamber of such diameter and length that the time of passage is approximately fifteen minutes.

The temperature is then reduced by passing through heat exchange to approximately 600 degrees Fahrenheit. While at this temperature, the mixture passes into a vent tank where the pressure is reduced to about 800 lbs.

per square inch, and part of the inert or I fixed gas may be vented off through suitable absorption medium in a third absorber, such as unused oil stock; The unvented product at a temperature of approximately 550 degrees Fahrenheit passes into a flash tower, where the pressure is reduced to 30 lbs. per square inch. The vapors from the flash tower pass to the fractionating tower, where gasoline or motor fuel at proper end point is fractionated out. This gasoline or motor fuel is preferably treated in the vapor phase by fullers earth. The Gray process of treatingis suitable for treating this type of vapor phase product. The bottoms from the fractionating tower and from the flash tower may be returned through suitable heat exchange as recycle stock.

The temperatures and pressures given in the specific example set forth have been found to give good results. \Vhen the pressures are r There are no residual tars; the tubes remain uncarboned; and carbon troubles experienced in processes heretofore employed are entirely eliminated. The motor fuel produced is of the highest anti-knock quality, of low Baum gravity and high volatility.

The invention will be more readily understood by reference to the accompanying drawings showing diagrammatically forms of apparatus which may be employed in carrying out my process.

In the drawings:

Fig. 1 is a diagrammatic view of a form of apparatus for carryingout the process in which the pressures of the reacting hydrocarbon and air are raised to the full pres sure prior to the reaction between said gases, and

Fig. 2 is a similar view showing an apparatus differing from Fig. 1 in that the pressures of the reacting hydrocarbon gas and air are raised to a pressure of 250300 lbs. per square inch prior to reaction between them, and the reaction product raised to a higher pressure prior to reaction of this product with the unoxidized hydrocarbon.

Referring to Fig. 1 of the drawings, the numeral 10 denotes an inlet pipe through which air or other oxidizing gas is admitted into the system through a suitable meter 11, and thence through pipe 11 successively through compressors 12, 1.3 and 14, where-' bv the pressure is raised preferably to about 100 to 1250 lbs. per square inch, and thence to a coil 15 heated by a gas flame or othersuitable means 16. Preferably steam is admitted to the coil 15 through pipe 17 controlled by valve 17'. After passing from the heating coil 15, the oxidizing gases under pressure are admitted to a reaction zone 18 through perforated pipes or nozzles 19, where they are brought into intimate contact with natural gas or other hydrocarbon admitted through similar perforated pipes 28. Preferably a platinum screen 28 is interposed between the two sets of perforated pipes 19 and 28 to serve as a catalyst for initiating the reaction between the hydrocarbon gas and the oxidizing gas. Preferably also a catalytic gas such as nitrous oxide is admitted to the reaction zone through pipe 19.

It is desirable that the hydrocarbon gas be heated entirely independently of the oxidizing gas and that both be supplied to the reaction zone under pressure.

, As shown, the natural gas is admitted through pipe 20, passing through a. suitable meter 21 and pipe 21, and successively through compressors 22, 23 and 24, where the pressure is raised preferably to around 1200 to 1250 lbs. per square inch, and thence by way of pipe 25 into a heating coil 26, heated by a burner 27, and thence into the reaction zone by way of the perforated pipes 28. The period of reaction is preferably a short one, varying from 1/100 of a second to one second, and after passing through this zone, the reaction products pass immediately into a constant temperature zone 29, wherein excess heat is removed by means of a heat interchange device including steam pipes 30. The purpose of this constant temperature zone is to prevent the reaction from proceeding too far, and by means of this control, the desired quality of product may be obtained. The oxidized products and inert gases pass from the constant temperature zone through pipe 31 controlled by valve 32 into a separator 34, which separator may be provided with a valved ofltake 35, whereby some of the liq uid from this separator may be removed and utilized if desired. The separator has also a vapor oiftake pipe 36 leading from the upper portion thereof, and a liquid ofl'take pipe 37 controlled by valve 3 leading from the bottom of the separator. A portion of the vapors passing from the separator through pipe 36 are led past valves 39 and 40 into an absorber 41, which absorber is provided with a vapor ofi'take 43 controlled by valve 43, through which nitrogen and other unabsorbed gases may be withdrawn. From the bottom of the absorber a pipe 44 leads to a mixing chamber 56. 4

Oil under pressure may be supplied to the absorber from an oil storage tank 45, through pipe 45 to pump 46, thence through pipe 42 containing valves and 49 to the top of the absorber. Another pipe 47 leads from the pump 46 to an auxiliary absorber 51. A valve 48 is placed in the pipe 47 to control the quantity of oil passing into the auxiliary absorber. A pipe 52 leads from the top of the absorber and is controlled by valve 53, the purpose of this being to permit nitrogen and other unabsorbed gases to pass from the auxiliary absorber. From the bot' tom of the absorber, oil passes through pipe 54 and pump 55 to the primary absorber 41 and then out through pipe 44. The auxiliary absorber does not function in the initial stage of operation, and its function will be described more fully hereinafter.

The pipe 44 leading from the bottom of the primary absorber conducts oil and oxidized hydrocarbons to a mixing chamber 56. Into this mixing chamber inert gases are injected through by-pass 57 and valve 58, these gases coming from the separator 34 without pass.- ing through the absorber. The purpose of adding these inert gases is to convert the mixture of oxidized hydrocarbon material and non-oxidized hydrocarbon material introduced through the pipe 44 into the full vapor phase. Preferably also, I admit into the mixing chamber 56 oxidized hydrocarbons withdrawn from the bottom of separator 34 through the pipe 37, the quantity of such material being regulated by the valve 38.

After a thorough admixture in the chamber 56, the products are passed through a heat exchanger 59, where the temperature is raised to a still higher degree.

After leaving the preheater 61, the products pass through a heating coil 62, preferably heated by a gas burner 63, and from the heater to a reaction chamber 64. From the chamber 64 a pipe 65 leads back to the heat exchanger 59, where the gaseous products are cooled, at the same time heating the products passing in the other direction through heat exchanger 59, as previously described. From the heat exchanger 59, the products are passed through pipe 66, venttank (al ready described in connection with Fig. 2) and pressure reducing valve 67, into a flash tower 66', where the pressure is reduced sulficiently to effect a rough separation of all the liquid materials falling within the range of motor fuel. The flash tower 66 is preferably provided with a pipe 67 leading to a safety valve 68. The tower has also av pipe 74 leading from the upper portion thereof and a pipe 70 leading from the lower portion, for returning liquid by way of pump 71, pipes 72 and 73, to the mixing chamber 56. the upper portion of the flash tower through reduced pressure valve 69 and pipe 7 4 to a fractionating tower 75. A liquid otltake 76 from the bottom of the fractionating tower leads throughpump 77 and pipes 72 and 73 to the mixing chamber 56. From the upper portion of the fractionating tower a pipe 78 conducts vapors to a vapor phase treater 79 of any suitable character, preferably containing fullers earth. A goose neck 80 connects the lower portion of the fractionating tower to the bottom of the vapor phase treatcr 79, and serves as a liquid seal, serving also to return the heavy liquid products to the system.

The vaporized materials pass off from n From this treating chamber 79 the vapors pass through a water cooled condenser 81 through pi e 82 to a suitable separating tank 83, where t e ressure is reduced sufiiciently to vent off higli artial pressure vapors, and also. nitrogen an other fixed gases through a pipe 85, pressure regulator 86, and thence through pipe 87 to the auxiliary absorber 51 previously described. In this auxlliary absorber the ases are stripped of normally liquid constituents by meeting a countercurrent of oil introduced through the p pe 47. The oil from the absorber, together with the absorbed material, is picked up and passed into the system by means of the pump 55 previously described. From the separator tank 83, motor fuel or other final product may be withdrawn through pipe 84 and passed to a place of storage or use.

While the o eration of the device 1S apparent from t e above description of the apparatus, the following detailed description may be of assistance in understand ng the functions of the various contributing elements of the system.

Air and gas are metered in a proportion of one part-of gas by volume to two and one-half parts of air. The pressure 15 elevated by means of the compressors to from 250 to 1200 to 1250 lbs. The gas and air passing through separate heating steps whlle under this compression is raised to from 350 to 900 degrees Fahrenheit, but preferably about 400 degrees Fahrenheit, where the pressure is approximately 1200 to 1250 lbs. -Where lower pressures are used,. the higher ranges of temperature should be employed.

A pressure of 1200 to 1250 lbs. per square inch is the optimum pressure and 1S preferably attained prior to the reaction zone, or if a lower pressure is initially employed, the

ressure may be subsequently raised to 7 around 1200 to 1250 lbs. per square inch as previously described.

The two gases are then contacted within the reaction zone 18, but previous to this contact a small amount of oxide of nitrogen and/0r steam is added to the air to act as a catalyst to initiate the reaction. The reaction takes place between the gases upon admixture, and this reaction may be further facilitated by the screen 28' containing sponge platinum inserted midway between the air and gas inlets 19 and 28. A. high temperature is produced within the reaction zone, which, if allowed to proceed without the dissipation of heat for more than one second, would result in the products going to carbon dioxide, carbon monoxide and water. Means for dissipating this heat of reaction are provided for by passing the re- I acting materials through a great number of small tubes surrounded by a steam jacket in the constanttemperature zone 29 under a without it.

pressure sufiicient to maintain a temperature around 500 to 550 degrees Fahrenheit. From this constant temperature zone 29, gases, vapors and liquid products of reaction pass without reduction of pressure through .the knock-out or separator 34, where a liquid material containing oxidized products separates out. The unliquefied material containing nitrogen from the top of the separator passes through the pipe36 and valve 39 under high pressure. Part of the fluid stream is diverted through valve 40 into the absorber 41, where it meets a stream of unoxidized oil entering through pipe 42, while another portion of the stream passes directly into the mixing chamber 56 through pipe 57 and valve 58 without passing through the absorber. The relative quantities and pressures of the fluids passing into the absorber and mixer respectively are obviously regulated by means of the valves 39, 40 and 58. The pressure within the mixing chamber and subsequent heating and reaction zones should preferably be maintained at not substantially less than 1200 lbs. per square inch. The oil passing from the absorber through pipe 44 is admixed with the liquid product entering through pipe 37 from the knock-out or separator 34, and the stream of vapors and gases isdiverted from pipe line 36- through valve 58 into the mixing chamber 56. Following this mixing chamber, the products pass through heat exchanger 59 and from thence they may be passed through steam preheater 61, in order to raise the temperature sufliciently to effect vaporization preliminary to entering the final stage of heating. This step may be dispensed with if the heat exchange is suflicient to effect this vaporization The mixture passing through the final stage of heating at 62 in the full vapor phase and still maintained under 1200 lbs. pressure, enters the unheated reaction chamber 64, where sufficient time (from 5 to 15 minutes) is allowed for the reaction prodnets to reach an optimum equilibrium for producing the maximum amount of motor fuel. From the reaction chamber 64, the products pass through the previously described heat exchanger 59, which is preliminary. to the steam preheater, and pass from this heat exchanger into the flash tower 66,, where the pressure is reduced sufficiently to efl'ect a rough separation of all the liquid materials falling within the range of motor fuel. This vaporized material then passes through the fractionating tower 75, where the gasoline is fractionated to the required end point. The liquid products from the bottom of the flash tower at and from the bottom of the fractionating tower at 76 are pumped back to the mixing chamber 56. The untreated vapors from the fractionating tower pass before condensation through vapor phase treatment with fullers earth,

at 79. The vapors from the fullers earth treatment ass .through Water cooled condenser 81 into tank 83, where the pressure is reduced sufliciently to vent ofi high partial pressure vapors, nitrogen and other fixed gases to the auxiliary absorber 51, where they are stripped of normally liquid constituents by meeting a counter-current stream of oil. The oil from the absorber, together with the absorbed material, is picked up and passed back into the system by means of pump 55 and repeats the cycle.

In the apparatus shown in Fig. 2, the arrangement of elements is the same as in Fig. 1, except that the gas and air are compressed to about 250-300 lbs. per square inch prior to their admission into reaction zone 18, and the vapors passing ofi from the separator 34 through pipe 36 are compressed to around 1200-4250 lbs. pressure in a subsequent stage of compression, which pressure is substantially maintained within the system up to and including the chamber 64, in which the oxidized and non-oxidized hydrocarbons are reacted. As shown, A and B denote air compressors, and C and D the gas compressors, by means of which pressure may be raised to an initial stage of compression, while E represents a compressor located Within pipe line 36 by means of which the pressure may be boosted to the final stage of compression, around 12001250 lbs. per square inch. Apart from the compressors A, B, C, D and E, the apparatus shown in Fig. 2 is the same as that in Fig. 1.

The character of the partially oxidized hydrocarbons within the chamber 34 is dependent on the pressure maintained within the reaction zone 18, which pressure may be varied considerably. The pressure maintained within those portions of the system in which reactions between the partially oxidized hydrocarbons and the non-oxidized hydrocarbons take place is, however, preferably not substantially less than 1200 lbs. per square inch, which pressure may either be attained in successive stages as illustrated in Fig. 2 or may be attained prior to the reaction zone 18 as described and illustrated in connection with Fig. 1.

It will be understood that the process has been described with specific reference to the production of motor fuel, as a desired end product. The process, however, is very flexible and by variations of operation which will be apparent to one skilled in the art, lighter, heavier, or intermediate products, such as kerosene, fuel oil and lubricating oil may be obtained.

Furthermore, valuable industrial products are obtained within the separator 34, which consists of partial oxidation products includ ing aldehydes, alcohols, acids, ketones and the like. These may be withdrawn through the ofitake 35 directly from the separator,

and may be employed for various industrial uses. These mixed products are useful without further purification for desulphurizatio'n of natural oils and natural gas frequently met with in certain oil fields. These partial oxidation products may be termed for convenience hydrocarbon oxides.

Pure oxidation products may be obtained by employing a special gas introduced at 20 instead of the mixture of gases contained in ordinary natural gas. By properly controlling conditions of time, temperature and pressure, the character and quality of the oxidation products may be controlled.

Likewise, while I preferably employ natural gas as one of the initial products undergoing treatment, nevertheless artificial gas, particularly a gas high in illuminants may be employed in place of the natural gas with certain modifications in the details of the process. Thus one of the important features of the invention is an improved oxidation process which is capable of complete control by reason of the fact that the temperatures and pressure of the hydrocarbon gas and the oxidizing gas are separately and in dependently regulated.

Other modifications of the process within the scope of the invention will be apparent to those skilled in the art.

What I claim is:

1. In a process for producing motor fuel by combining an oxidized hydrocarbon and an unoxidized hydrocarbon by the aid of heat and pressure, the step which comprises preparing the oxidized hydrocarbon by compressing and subsequently heating a normally gaseous hydrocarbon and an oxygencarrying gas separately and then contacting the two gases in a reaction chamber exterior to the zone of compression while under pressure substantially above atmospheric and without prior admixture of the gases.

2. In a process as herein described, the improvement in oxidizing natural gas, which comprises preheating the natural gas and an oxygenating gas separately and under pressure, then immediately contacting the two gases in a reaction chamber separate from the zone of compression without prior admixture of the gases for a period of from 1/100 of .a second to one second, and removing excess heat from the mixture.

3. An improved synthetic and addition process of partially oxygenating a normally gaseous hydrocarbon, which comprises preheating the hydrocarbon gas and an oxidizing gas separately and subsequently reacting the two gases in a chamber separate from the heating zone to produce liquid partial oxidation products in a single step directly from the original constituents.

4. An improved synthetic and addition process of partially oxygenating a normally gaseous hydrocarbon which comprises preheating the hydrocarbon gas and an oxidizing as. separately and subsequently reacting t e two gases in a chamber separate from the heating zone, controlling the temperatures of the reacting gases to prevent overheating, and controlling the time of the reaction to produce liquid artialoxidation products in a single step 'rectly from the original constituents.

5. A conversion process of the character described, which comprises mixing a normally liquid, partially oxidized hydrocarbon with a normally liquid, unoxidized hydrocarbon under heat and pressure, and adding to the mixture sufiicient inert gas such as nitrogen,

to produce the full vapor phase under approximately 1200 pounds pressure per square inch, preliminary to the final stage of heating under substantially the same pressure, then heating the entire mixture fully in vapor phase to produce hydrocarbon compounds of a difierent nature than the original materials. A

6. A process of producing motor fuel comprising separately compressing and then heating a hydrocarbon 1n the vapor phase and an oxygen-carrying gas, then reacting the gases in a zone separate from the heating zone without reduction of pressure, limiting the reaction ppriod to from 1/100 to one second of time, maintaining the temperature of the reaction substantially constant, and the pressure at substantially. 1200 lbs., adding a non-oxidized hydrocarbon in separate absorbing and mixing steps, adding to the mixture suflicient inert gas under pressure of approximately 1200 pounds per square inch to produce the full vapor phase of all constituents preliminary to a final stage of heating, heating the mixture under substantially the same pressure and after the final stage of heating, continuously passing the entire m xtureinto a reaction chamber, maintaining saidmixture in the reaction zone in the vapor phase for a suflicient time to allow for complete conversion and equilibrium, cooling the reaction products, reducing the pressure fol lowing the cooling step, further reducing the pressure in a separate zone for the purpose of separating the more volatile and less volatile products of reaction, and returning the less volatile products to the system as recycle stock.

7. A process of oxidizing natural gas which comprises separately and independently heating and compressing the natural gas and an. oxidizing gas, then combining the two gases in a closed chamber separate from and independent of the compression zone, regulating the temperature of the reaction, and then separating the liquid and vapor products of the reaction. a

8. A process for producing motor fuel by combinin a normally liquid, partially oxidized hy rocarbon and an unoxidized hydrocarbon which comprises initially reparing the partially oxidized hydrocarbon by heating an uncracked gaseous hydrocarbon and an pxygen-carrymg gas separately and contactmg the two gases in a reaction chamber .under pressure substantially above atmospheric and then combining the reaction product with the unoxidized hydrocarbon by the aid of heat and pressure.

9. A process for producing motor fuel by combining a normally liquid, partially 0x1- dlzed hydrocarbon and an unoxidized hydrocarbon the step which comprises initially preparing the partially oxidized hydrocarbon by eatm a chemically saturated gaseous hydrocar on and an oxygen-carrying gas separately and contacting the two gases in a reaction chamber under pressure substantially above atmospheric and then combining the reaction product with the unoxidized hydrocarbon by the aid of heat and pressure.

' 10. A process for producing motor fuel by combining a normally liquid, partially 0x1- dized hydrocarbon and an unoxidized hydrocarbon which comprises initially preparing the partially oxidized hydrocarbon by heating an uncracked gaseous hydrocarbon and an oxygen-carrying gas separately and contacting the two gases in a reaction chamber under pressure substantially above atmospheric and without prior admixture and then combining the reaction product with the unoxidized hydrocarbon by the aid of heat and pressure.

11. The conversion process for producing motor fuel comprising mixing a normally liquid, partially oxidized hydrocarbon and a non-oxidized hydrocarbon under pressure, adding an inert gas to the mixture while-under pressure of approximately 1200 lbs. to produce a full vapor phase, and subjecting the entire mixture without reduction of pressure to a temperature of approximately 785 Fahrenheit while fully in vapor. phase in order to produce conversion of the constituents usedinto low boiling hydrocarbons including a motor fuel fraction.

12. A process for producing normally liquid, partially oxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a single reaction step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate from the zones of compression.

13. A process for producing normally liquid, partially oxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a single reaction step from the original constituents, which process comh hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate from the zones of compression, and controlling the temperature of the reaction.

14. A process for producing normally liquid, partiallyoxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a. single reaction step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through areaction zone separate from the zones of compression, and limiting the period of the reaction to from 1/100 to 1 second.

15. A process for producing normally liquid, partially oxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a single reaction step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate from the zones of compression, and maintaining a temperature of approximately 400 F. within the reaction zone.

16, A process for producing normally liquid, partially oxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a single reaction step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate from the zones of compression, and admitting N0 to the reaction zone.

17. A process for producing normally liquid, partially oxid'zing hydrocarbons from normally gaseous hydrocai ons and an oxidizing gas in a single react .on step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate from the zones of compression, the reaction being carried out in the presence of a platinum catalyst.

18. In a process for producing motor fuel by combining a partially oxidized hydrocarbon and an unoxidized hydrocarbon, the

step which comprises preparing the oxidized hydrocarbon by compressing and subsequently heating a normally gaseous hydrocarbon, and separately compressing and subsequently heating an oxygen-carrying gas, and then contacting the two gases while still under pressure greater than atmospheric in a re action zone separate from the zones of compression Without prior admixture of the gases.

19. In a process as herein described, the improvement which comprises compressing and heating a normally gaseous hydrocarbon, and separately compressing and heating an oxygen-carrying gas, then passing the two gases without reduction of pressure into and continuously through a reaction zone separate from the zones of compression without admixture of the gases prior to the reaction zone, and controlling the period and temperature of the reaction to produce a normally liquid, partially oxidized hydrocarbon mixture from the original constitutents in asingle step.

20. A process for producing motor fuel by combining a partially oxidized, normally liquid hydrocarbon and an unoxidized liquid hydrocarbon, which comprises initially preparing the partially oxidized hydrocarbon by compressing and heating a normally gaseous hydrocarbon, and separately compressing and heating an oxygen-carrying gas, then contacting the two gases in a reaction zone separate from the zones of compression while still under pressure without admixture of the gases prior to their entrance into the reaction zone, and then combining the partially oxidized hydrocarbon obtained by such reaction with the unoxidized liquid hydrocarbon with the aid of heat and pressure.

21. A process for producing motor fuel, which comprises adding normally liquid, partially oxidized hydrocarbons to unoxidized, normally liquid hydrocarbons, converting the entire mixture into the full vapor phase under pressure substantially greater than atmospheric, and producing a reaction between the two constituents by the aid of heat and pressure while fully in the Vapor phase.

22. A conversion process for producing motor fuel, which comprises adding normally liquid partially oxidized hydrocarbons to unoxidized, normally liquid hydrocarbons, adding an inert gas, converting the entire mixture into full vapor phase under :1 pressure substantially greater than atmospheric, and producing a reaction between the two constitutents by the aid of heat'and high super-atmospheric pressure while fully in vapor phase.

23. A porcess for producing motor fuel by combining a normally gaseous hydrocarbon and a normally liquid hydrocarbon, which comprises producing a normally liquid, par

tially oxidized hydrocarbon by reacting the gaseous hydrocarbon with an oxidizing gas under controlled temperature and pressure conditions, then admixing the partially oxidized liquid hydrocarbon with the non-oxidized hydrocarbon, adding an inert gas and converting the entire mixture into the full vapor phase under pressure of approximately 1200 lbs. per square inch, then reacting the constituents while fully in vapor phase without reduction of pressure at a temperature of approximately 785 F. for a period sufficient to allow substantially complete conversion and equilibrium of the constituents.

24. A continuous process for producing motor fuel by reacting a normally liquid, partially oxidized hydrocarbon and an unoxidized hydrocarbon, which comprises initially preparing the partially oxidized hydrocarbon by continuously reacting a normally gaseous hydrocarbon and an oxygen-carrying gas by the aid of heat and pressure, continuously separating the gaseous portions of the partial oxidation product from the liquid portions, continuously stripping the low pressure gases from the gaseous portion by contacting the gaseous portion with incoming non-oxidized liquid hydrocarbon, and then combining the non-oxidized and the partially oxidized liquid hydrocarbons with the aid of heat and pressure while fully in vapor phase.

25. A process for producing normally liquid, partially oxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a single reaction step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate from the zones of compression, and admitting an oxide of nitrogen to the reaction zone.

26. A process for producing normally liquid, partially oxidized hydrocarbons from normally gaseous hydrocarbons and an oxidizing gas in a single reaction step from the original constituents, which process comprises compressing and heating the gaseous hydrocarbon, and separately compressing and heating the oxidizing gas, then passing the two gases without prior admixture and without reduction of pressure directly into and continuously through a reaction zone separate fromthe zones of compression, the reaction being carried out in the presence of a catalyst.

27. The herein-described process which comprises mixing a normally liquid, partially oxidized hydrocarbon with an unoxidized liquid hydrocarbon, continuously passing the entire mixture while under elevated temperature and pressure of not less than approximately 1200 lbs. per square inch through a heating and reaction zone, and producing a conversion of the entire mixture into low boiling hydrocarbons including the motor fuel fraction without removal of any portion prlor to the completion of the conversion in the reaction zone.

28. A conversion process of the character described, comprising mixing a normally liquid, partially oxidized hydrocarbon and a non-oxidized hydrocarbon under superatmospheric pressure, transforming the entire mixture while under superatmospheric pressure into the full vapor phase, and sub'ecting the entire mixture under superatmosp eric pressure while fully in vapor phase to an elevated temperature sufiicient to produce substantially complete conversion of the constituents used into lower boiling point hydrocarbons including the motor fuel fraction.

29. A conversion process of the character described, comprising mixing a normally liquid, partially oxidized hydrocarbon and a non-oxidized hydroc..rbon under superatmospherlc pressure, transforming the entire mixture while under pressure into the full vapor phase by the addition of an inert gas with the aid of heat, and subjecting the entire-mixture under superatmospheric pressure while fully in vapor phase to an elevated temperature suflicient to produce substantially complete conversion of the constituents used into lower boiling point hydrocarbons including the motor fuel fraction.

30. A continuous conversion processof the character described, comprising mixing a normally liquid, partially oxidized hydrocarbon and a non-oxidized hydrocarbon under superatmospheric pressure, transforming the entire mixture while under superatmospheric pressure into the full vapor phase by the addition of an inert gas with the aid of heat, continuously passing the entire mixture while in full vapor phase into a reaction zone, and subjecting the entire mixture under superatmospheric pressure to an elevated temperature suficient to produce substantially complete conversion of the hydrocarbon constituents used into lower boilin point hydrocarbons including the motor uel fraction.

31. A process as in claim 30 in which a pressure of approximately 1200 lbs. per square inch is maintained during the conversion reaction.

32. A process as in claim 30 in which the mixture while in vapor phase is heated to approximately 785 F.

In testimony whereof-I aflix my signature.

ISAAC N. BEALL.

DISCLAIMER 1,859,193.Isaac N. Beall, Washington, D. C. OIL AND NATURAL GAS CONVER- SION PRocEss. Patent dated May 17, 1932. Disclaimer filed October 22, 193%, by the assignee, John C. W. Beall, the patentee, Isaac N. Beall, concurring. Hereby enters this disclaimer limiting said claims of said patent as follows, to-wit: 1-. From the scope of claim 3 he disclaims any interpretation except that wherein the medium for heating the oxidizing gas is separate and apart from the medium for heating the hydrocarbon gas and wherein said gases are initially contacted or brought together in the reaction chamber without prior admixture of the original constituents. 2. From the scope of claims 4 and 7 he disclaims any interpretation of separately and independently heating and compressing the natural gas and an oxidizing gas except that wherein the medium of heat supply for the natural gas is separate and apart from the medium'of heat supply for the oxidizing gas and wherein the heat instantly generated by the initial contacting of the unmixed gases in the reaction zone is then subjected to a regulation to instantly check or control the reaction time to prevent overheating. v

[Oflicz'al Gazette January 29, 1.985.] 

